Positive photosensitive resin composition, photosensitive resin film prepared by using the same, and semiconductor device including the photosensitive resin film

ABSTRACT

Disclosed are a positive photosensitive resin composition that includes (A) a polybenzoxazole precursor including a first polybenzoxazole precursor including a repeating unit represented by the following Chemical Formula 1 and a repeating unit represented by the following Chemical Formula 2, and having a thermally polymerizable functional group at at least one of the terminal end; (B) a dissolution controlling agent including a novolac resin including a repeating unit represented by the following Chemical Formula 4; (C) a photosensitive diazoquinone compound; (D) a silane compound; (E) an acid generator; and (F) a solvent, a photosensitive resin film prepared using the same, and a semiconductor device including the photosensitive resin film.

CROSS-REFERENCE TO RELATED APPLICATION

This application claims priority to and the benefit of Korean PatentApplication No. 10-2011-0126315 filed in the Korean IntellectualProperty Office on Nov. 29, 2011, the entire disclosure of which isincorporated herein by reference.

FIELD

This disclosure relates to positive photosensitive resin composition,photosensitive resin film prepared using the same, and a semiconductordevice including the photosensitive resin film.

BACKGROUND

Liquid crystal displays (LCDs) are widely available as flat paneldisplays. Recently organic light emitting diodes (OLEDs) have drawnattention as devices which can have high luminance and full colordisplay.

Organic light emitting display devices include organic light emittingdiodes including a hole injection electrode and an organic emissionlayer, and an electron injection electrode. Each organic light emittingdiode emits light by energy generated when exciton produced by bindingelectrons and holes in the organic emission layer falls from the exitedstate into the ground state, and the organic light emitting diode (OLED)display displays the predetermined image by using the light emitting.For example, in order to provide a pixelated organic light emittingdiode (OLED) display such as a television, a computer monitor, a mobilephone display, or a digital camera display, each organic light emittingdiode may be arranged as a pixel having a matrix format. The pixels maybe fabricated to emit the same color, so as to provide a monocolordisplay device; or the pixels may be fabricated to emit variousdifferent colors, for example to provide a red, green, and blue displaydevice. The organic light emitting diode is self light emitting type, soa backlight unit for emitting light is not required unlike a liquidcrystal display (LCD). Thereby, the thickness and the weight thereof maybe reduced to a level of about 30% of the liquid crystal display.

Polyimide resins have received attention as an insulation layer materialfor the organic light emitting display device. Polyimide resins can haveexcellent heat resistance and stability at processes conducted at atemperature above 200° C., excellent mechanical strength, and a lowdielectric constant (low-k). Polyimide resins can also provide smoothcoating surfaces, lower the amount of impurities, which may deterioratethe reliability of device, and easily provide a fine pattern.

The conventional method of manufacturing an insulation layer or asemiconductor protective layer of an organic light emitting displaydevice using the polyimide includes an additional photoresist processincluding, for example, etching with an organic solvent afterpatterning. Thus, the process is complicated; the cost is increased; theenvironment is contaminated by using the organic solvent; and the resistpattern may be swelled. In order to solve these problems, a negativephotosensitive polyimide in which the etching solution is substitutedwith an alkali aqueous solution has been researched. However, in thiscase, the patterning can be deteriorated by non-crosslinked residue inthe exposed region during the development, so that it can be difficultto achieve high resolution. Therefore, there is a need to develop apositive photosensitive polyimide which may achieve high-resolution.

Positive photosensitive resin compositions can have advantages such asproviding a high contrast between the exposure part and non-exposed partby the interaction of novolac resin and a photo-sensitive agent. Heatresistance, however, is relatively low, so the pattern maintainingperformance may be too decreased to ensure reliability.

In order to solve these problems, novolac resin can be mixed withpolyamic acid or a polyamic acid-polyimide copolymer or the like andassociated with a photo-sensitive agent of diazonaphtoquinone. It canstill be difficult, however, to achieve high resolution and highsensitivity since the dissolubility difference of between an exposedregion and non-exposed region is not controlled.

Accordingly, there is still a need for a positive photosensitive resincomposition that can provide easy control of the dissolubility to thealkali aqueous solution of an exposed region and non-exposed region andthat can provide excellent chemical resistance and heat resistance andhigh sensitivity.

SUMMARY OF THE INVENTION

One embodiment provides a positive photosensitive resin composition thatcan have excellent sensitivity, resolution, pattern shaping properties,residue removal properties, and reliability by including apolybenzoxazole precursor having a predetermined functional group and adissolution controlling agent including a novolac resin having apredetermined structure.

Another embodiment provides a photosensitive resin film prepared usingthe positive photosensitive resin composition.

Yet another embodiment provides a semiconductor device including thephotosensitive resin film.

According to one embodiment, provided is a positive photosensitive resincomposition that includes (A) a polybenzoxazole precursor including afirst polybenzoxazole precursor including a repeating unit representedby the following Chemical Formula 1 and a repeating unit represented bythe following Chemical Formula 2, and having a thermally polymerizablefunctional group at at least one of the terminal end; (B) a dissolutioncontrolling agent including a novolac resin including a repeating unitrepresented by the following Chemical Formula 4; (C) a photosensitivediazoquinone compound; (D) a silane compound; (E) an acid generator; and(F) a solvent.

In Chemical Formulae 1 and 2,

X¹ is the same or different in each repeating unit and is eachindependently a substituted or unsubstituted C6 to C30 aromatic organicgroup, a substituted or unsubstituted tetravalent to hexavalent C1 toC30 aliphatic organic group, or a substituted or unsubstitutedtetravalent to hexavalent C3 to C30 alicyclic organic group,

X² is the same or different in each repeating unit and is eachindependently a functional group represented by the following ChemicalFormula 3, and

Y¹ and Y² are the same or different and are each independently asubstituted or unsubstituted C6 to C30 aromatic organic group, asubstituted or unsubstituted divalent to hexavalent C1 to C30 aliphaticorganic group, or a substituted or unsubstituted divalent to hexavalentC3 to C30 alicyclic organic group.

In Chemical Formula 3,

Z¹ is the same or different in each repeating unit and is eachindependently a single bond, —O—, —COO—, —COO—, —NH—, —CONH—,substituted or unsubstituted C1 to C15 alkylene, substituted orunsubstituted C2 to C15 alkenylene, or substituted or unsubstituted C2to C15 alkynylene,

G¹ is the same or different in each repeating unit and is eachindependently a single bond, a substituted or unsubstituted C6 to C30aromatic organic group, a substituted or unsubstituted divalent tohexavalent C3 to C30 alicyclic organic group, or a substituted orunsubstituted divalent to hexavalent C2 to C30 heterocyclic group,

R¹ is the same or different in each repeating unit and is eachindependently hydrogen, fluorine, a hydroxyl group, a thiol group, asubstituted or unsubstituted C1 to C30 carboxyl group, or a substitutedor unsubstituted C1 to C30 aliphatic organic group,

each R² is the same or different in each repeating unit and is eachindependently hydrogen, substituted or unsubstituted C1 to C30 alkyl, asubstituted or unsubstituted C1 to C30 carboxyl group, a hydroxy group,or a thiol group,

n₁ is an integer ranging from 1 to 5, and

n₂ is an integer ranging from 0 to 3.

In Chemical Formula 4,

R³ is the same or different in each repeating unit and is a substitutedor unsubstituted C1 to C20 aliphatic organic group,

Greater than or equal to about 50 mol % of R³ based on 100 mol % of R³in a repeating unit included in the novolac resin may be present in ameta position with respect to a hydroxy group (OH).

In one embodiment, the functional group represented by the aboveChemical Formula 3 may include one selected from functional groupsrepresented by the following Chemical Formulae 7 to 14 and combinationsthereof.

In Chemical Formulae 7 to 14,

R⁷, R⁸, R¹⁰, R¹², R¹⁴, R¹⁶ and R¹⁸ are the same or different in eachrepeating unit and are each independently hydrogen, fluorine, a hydroxygroup, a thiol group, a substituted or unsubstituted C1 to C30 carboxylgroup, or a substituted or unsubstituted C1 to C30 aliphatic organicgroup,

R⁹, R¹¹, R¹³, R¹⁵, R¹⁷, R¹⁹, R²⁰ and R²¹ are the same or different ineach repeating unit and are each independently hydrogen, substituted orunsubstituted C1 to C30 alkyl, a substituted or unsubstituted C1 to C30carboxyl group, a hydroxy group, or a thiol group,

n₉, n₁₁ and n₁₃ are each independently an integer ranging from 0 to 11,and

n₆, n₇, n₈, n₁₀, n₁₂, n₁₄, n₁₅ and n₁₆ are each independently an integerranging from 0 to 3.

Greater than or equal to about 60 mol % of R³ based on 100 mol % of R³in a repeating unit included in the novolac resin may be present in ameta position with respect to a hydroxy group (OH).

Greater than or equal to about 90 mol % of R³ based on 100 mol % of R³in a repeating unit included in the novolac resin may be present in ameta position and a para position with respect to a hydroxy group (OH).

R³ in a repeating unit included in the novolac resin may have a moleratio of presenting in a meta position (R³ _(m)) and presenting in apara position (R³ _(p)) of about 5:5 to about 10:0, for example, about6:4 to about 9:1.

Examples of the solvent may include without limitation γ-butyrolactone,ethyl lactate, propyleneglycol monomethylether, and the like, andcombinations thereof.

The first polybenzoxazole precursor may include a repeating unitrepresented by above Chemical Formula 1 and a repeating unit representedby above Chemical Formula 2 at a mole ratio of about 60:40 to about95:5.

The first polybenzoxazole precursor may have a weight average molecularweight (Mw) of about 4,000 g/mol to about 20,000 g/mol.

The polybenzoxazole precursor may further include a secondpolybenzoxazole precursor including a repeating unit represented by thefollowing Chemical Formula 33, and having a thermally polymerizablefunctional group at at least one of the terminal end.

In Chemical Formula 33,

X⁴ is the same or different in each repeating unit and is eachindependently a substituted or unsubstituted C6 to C30 aromatic organicgroup, a substituted or unsubstituted tetravalent to hexavalent C1 toC30 aliphatic organic group, or a substituted or unsubstitutedtetravalent to hexavalent C3 to C30 alicyclic organic group, and

Y⁴ is the same or different in each repeating unit and is eachindependently a substituted or unsubstituted C6 to C30 aromatic organicgroup, a substituted or unsubstituted divalent to hexavalent C1 to C30aliphatic organic group, or a substituted or unsubstituted divalent tohexavalent C3 to C30 alicyclic organic group.

The second polybenzoxazole precursor may have a weight average molecularweight (Mw) of about 4,000 g/mol to about 20,000 g/mol.

The polybenzoxazole precursor may include the first polybenzoxazoleprecursor and the second polybenzoxazole precursor at a weight ratio ofabout 5:95 to about 95:5.

The positive photosensitive resin composition may include about 1 partby weight to about 30 parts by weight of the dissolution controllingagent (B); about 5 parts by weight to about 100 parts by weight of thephotosensitive diazoquinone compound (C); about 0.1 parts by weight toabout 30 parts by weight of the silane compound (D); about 0.1 parts byweight to about 20 parts by weight of the acid generator (E); and about50 parts by weight to about 900 parts by weight of the solvent (F) basedon about 100 parts by weight of the polybenzoxazole precursor (A).

According to another embodiment of the present invention, aphotosensitive resin film fabricated the positive photosensitive resincomposition is provided.

According to a further embodiment of the present invention, asemiconductor device including the photosensitive resin film isprovided.

The semiconductor device may be an organic light emitting diode (OLED)or a liquid crystal display (LCD).

By using a positive photosensitive resin composition including apolybenzoxazole precursor having a predetermined functional group and adissolution controlling agent including a novolac resin having apredetermined structure, the dissolution controlling effect may beimproved; mechanical properties and reliability of films may beimproved; excellent sensitivity, resolution, pattern shaping properties,and residue removal properties may be obtained; and moistureabsorptivity may be decreased.

DETAILED DESCRIPTION

The present invention will be described more fully hereinafter in thefollowing detailed description of the invention, in which some but notall embodiments of the invention are described. Indeed, this inventionmay be embodied in many different forms and should not be construed aslimited to the embodiments set forth herein; rather, these embodimentsare provided so that this disclosure will satisfy applicable legalrequirements.

As used herein, when a specific definition is not otherwise provided,the term “substituted” may refer to one substituted with at least onesubstituent comprising halogen (—F, —Br, —Cl, or —I), a hydroxy group, anitro, a cyano group, an amino group (NH₂, NH(R²⁰⁰), or N(R²⁰¹)(R²⁰²)),wherein R²⁰⁰, R²⁰¹ and R²⁰² are the same or different and areindependently C1 to C10 alkyl), an amidino group, a hydrazine group, ahydrazone group, a carboxyl group, substituted or unsubstituted alkyl,substituted or unsubstituted alkenyl, substituted or unsubstitutedalkynyl, a substituted or unsubstituted alicyclic organic group,substituted or unsubstituted aryl, substituted or unsubstitutedheterocyclic group, or a combination thereof.

As used herein, when a specific definition is not otherwise provided,the term “alkyl” may refer to a C1 to C30 alkyl, for example C1 to C15alkyl, the term “cycloalkylene” may refer to C3 to C30 cycloalkylene,for example C3 to C18 cycloalkylene, the term “alkoxy” may refer to C1to C30 alkoxy, for example C1 to C18 alkoxy, the term “aryl” may referto C6 to C30 aryl, for example C6 to C18 aryl, the term “alkenyl” mayrefer to C2 to C30 alkenyl, for example C2 to C18 alkenyl, the term“alkylene” may refer to C1 to C30 alkylene, for example C1 to C18alkylene, and the term “arylene” may refer to C6 to C30 arylene, forexample C6 to C18 arylene.

As used herein, when a specific definition is not otherwise provided,the term “aliphatic organic group” may refer to C1 to C30 alkyl, C2 toC30 alkenyl, C2 to C30 alkynyl, C1 to C30 alkylene, C2 to C30alkenylene, or C2 to C30 alkynylene, for example C1 to C15 alkyl, C2 toC15 alkenyl, C2 to C15 alkynyl, C1 to C15 alkylene, C2 to C15alkenylene, or C2 to C15 alkynylene, the term “alicyclic organic group”may refer to C3 to C30 cycloalkyl, C3 to C30 cycloalkenyl, C3 to C30cycloalkynyl, C3 to C30 cycloalkylene, C3 to C30 cycloalkenylene, or C3to C30 cycloalkynylene, for example C3 to C15 cycloalkyl, C3 to C15cycloalkenyl, C3 to C15 cycloalkynyl, C3 to C15 cycloalkylene, C3 to C15cycloalkenylene, or C3 to C15 cycloalkynylene, the term “aromaticorganic group” may refer to C6 to C30 aryl or C6 to C30 arylene, forexample C6 to C16 aryl or C6 to C16 arylene, the term “heterocyclicgroup” may refer a C2 to C30 heterocycloalkyl, C2 to C30heterocycloalkylene, C2 to C30 heterocycloalkenyl, C2 to C30heterocycloalkenylene, C2 to C30 heterocycloalkynyl, C2 to C30heterocycloalkynylene, C2 to C30 heteroaryl, or C2 to C30 heteroarylenethat include 1 to 3 heteroatoms comprising O, S, N, P, Si, or acombination thereof in one ring, for example C2 to C15 heterocycloalkyl,C2 to C15 heterocycloalkylene, C2 to C15 heterocycloalkenyl, C2 to C15heterocycloalkenylene, C2 to C15 heterocycloalkynyl, C2 to C15heterocycloalkynylene, C2 to C15 heteroaryl, or C2 to C15 heteroarylenethat include 1 to 3 heteroatoms comprising O, S, N, P, Si, or acombination thereof in one ring.

As used herein, when a specific definition is not otherwise provided,the term “combination” refers to mixing or copolymerization. Also, theterm “copolymerization” refers to block copolymerization, randomcopolymerization or graft copolymerization, and the term “copolymer”refers to a block copolymer, a random copolymer, or graft copolymer.

Also, “*” refers to a linking part between the same or different atoms,or chemical Formulae.

According to one embodiment, a positive photosensitive resin compositionincludes (A) a polybenzoxazole precursor including a firstpolybenzoxazole precursor including a repeating unit represented by thefollowing Chemical Formula 1 and a repeating unit represented by thefollowing Chemical Formula 2, and having a thermally polymerizablefunctional group at at least one of the terminal end, (B) a dissolutioncontrolling agent including a novolac resin including a repeating unitrepresented by the following Chemical Formula 4, (C) a photosensitivediazoquinone compound, (D) a silane compound, (E) an acid generator, and(F) a solvent.

In Chemical Formulae 1 and 2,

X¹ is the same or different in each repeating unit and is eachindependently a substituted or unsubstituted C6 to C30 aromatic organicgroup, a substituted or unsubstituted tetravalent to hexavalent C1 toC30 aliphatic organic group, or a substituted or unsubstitutedtetravalent to hexavalent C3 to C30 alicyclic organic group,

X² is the same or different in each repeating unit, and is independentlya functional group represented by the following Chemical Formula 3, and

Y¹ and Y² are the same or different and are each independently asubstituted or unsubstituted C6 to C30 aromatic organic group, asubstituted or unsubstituted divalent to hexavalent C1 to C30 aliphaticorganic group, or a substituted or unsubstituted divalent to hexavalentC3 to C30 alicyclic organic group.

In Chemical Formula 3,

Z¹ is the same or different in each repeating unit and is eachindependently a single bond, —O—, —COO—, —COO—, —NH—, —CONH—,substituted or unsubstituted C1 to C15 alkylene, substituted orunsubstituted C2 to C15 alkenylene, or substituted or unsubstituted C2to C15 alkynylene, and in one embodiment, Z¹ is a single bond, —O—,—COO—, or C1 to C5 alkylene.

G¹ is the same or different in each repeating unit and is eachindependently a single bond, a substituted or unsubstituted C6 to C30aromatic organic group, a substituted or unsubstituted divalent tohexavalent C3 to C30 alicyclic organic group, or a substituted orunsubstituted divalent to hexavalent C2 to C30 heterocyclic group, andin one embodiment, the aromatic organic group, alicyclic organic groupand heterocyclic group may include at least one ring.

R¹ is the same or different in each repeating unit and is eachindependently hydrogen, fluorine, a hydroxy group, a thiol group, asubstituted or unsubstituted C1 to C30 carboxyl group, or a substitutedor unsubstituted C1 to C30 aliphatic organic group.

each R² is the same or different in each repeating unit and is eachindependently hydrogen, substituted or unsubstituted C1 to C30 alkyl, asubstituted or unsubstituted C1 to C30 carboxyl group, a hydroxy group,or a thiol group.

n₁ is an integer ranging from 1 to 5, and

n₂ is an integer ranging from 0 to 3.

Sometime the functional group represented by above Chemical Formula 3may partially include a hydrophilic group, but it is generallyhydrophobic, so as to suppress the dissolution of the positivephotosensitive resin composition to the alkali developing solution.

When the positive photosensitive resin composition includes the firstpolybenzoxazole precursor including a functional group represented byabove Chemical Formula 3, the dissolubility to the alkali developingsolution may be effectively controlled in the exposed part and thenon-exposed part. Thereby, the film residue ratio and the patternshaping properties of film fabricated by using the positivephotosensitive resin composition may be improved, and the residue may beeffectively removed without scum to improve the residue removalproperties. In addition, the mechanical properties, the reliability, thesensitivity and the resolution of film fabricated by using the positivephotosensitive resin composition may be also improved.

In Chemical Formula 4,

R³ is the same or different in each repeating unit and is a substitutedor unsubstituted C1 to C20 aliphatic organic group, in one embodiment,substituted or unsubstituted C1 to C20 alkyl, and in another embodiment,methyl.

Greater than or equal to about 50 mol % of R³ based on 100 mol % of R³in a repeating unit included in the novolac resin may be present in ameta position with respect to a hydroxy group (OH).

When the positive photosensitive resin composition includes the novolacresin, in the non-exposed part, the hydroxyl group of novolac resinforms a hydrogen bond with a polybenzoxazole precursor and aphotosensitive diazoquinone compound, and R³ of the novolac resin isnon-polar, so the non-exposed part is not well dissolved in an alkalideveloping solution. On the other hand, the exposed part has polarityincreased by a photosensitive diazoquinone compound, and thus, is welldissolved in an alkali developing solution. In this way, since theunexposed part is controlled to be non-polar, and the exposed part iscontrolled to be polar, the exposed part may have effectively improvedalkali developability, sensitivity, and film residue ratio.

Non-polarity and polarity of the positive photosensitive resincomposition may be identified by measuring a contact angle relative towater. Specifically, an unexposed part may have a contact angle relativeto water in a range of about 65° to about 80°, and an exposed part mayhave a contact angle relative to water in a range of about 35° to about60°.

The polybenzoxazole precursor is cross-linked with the novolac resinduring thermal curing, and mechanical strength of a film fabricatedusing a positive photosensitive resin composition and residue removalproperties may be improved.

As a result, the positive photosensitive resin composition may haveexcellent sensitivity, resolution, film residue ratios, pattern shapingproperties and residue removal properties, and a photosensitive resinfilm fabricated using the positive photosensitive resin composition mayhave excellent mechanical properties.

The positive photosensitive resin composition may include (G) one ormore other additives.

Hereinafter, each composition component is described in detail.

(A) Polybenzoxazole Precursor

The polybenzoxazole precursor may include the first polybenzoxazoleprecursor including the repeating unit represented by the above ChemicalFormula 1 and the repeating unit represented by the above ChemicalFormula 2, and having a thermally polymerizable functional group at atleast one of the terminal end.

In Chemical Formula 1, X¹ is the same or different in each repeatingunit, and is each independently an aromatic organic group, a tetravalentto hexavalent aliphatic organic group, or a tetravalent to hexavalentalicyclic organic group. In one embodiment, X¹ is the same or differentin each repeating unit, and is each independently an aromatic organicgroup, or a tetravalent to hexavalent alicyclic organic group.

Specifically, X¹ may be a residual group derived from an aromaticdiamine.

Examples of the aromatic diamine may include without limitation3,3′-diamino-4,4′-dihydroxybiphenyl,4,4′-diamino-3,3′-dihydroxybiphenyl,bis(3-amino-4-hydroxyphenyl)propane,bis(4-amino-3-hydroxyphenyl)propane,bis(3-amino-4-hydroxyphenyl)sulfone,bis(4-amino-3-hydroxyphenyl)sulfone,2,2-bis(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane,2,2-bis(4-amino-3-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane,2,2-bis(3-amino-4-hydroxy-5-trifluoromethylphenyl)hexafluoropropane,2,2-bis(3-amino-4-hydroxy-6-trifluoromethylphenyl)hexafluoropropane,2,2-bis(3-amino-4-hydroxy-2-trifluoromethylphenyl)hexafluoropropane,2,2-bis(4-amino-3-hydroxy-5-trifluoromethylphenyl)hexafluoropropane,2,2-bis(4-amino-3-hydroxy-6-trifluoromethylphenyl)hexafluoropropane,2,2-bis(4-amino-3-hydroxy-2-trifluoromethylphenyl)hexafluoropropane,2,2-bis(3-amino-4-hydroxy-5-pentafluoroethylphenyl)hexafluoropropane,2-(3-amino-4-hydroxy-5-trifluoromethylphenyl)-2-(3-amino-4-hydroxy-5-pentafluoroethylphenyl)hexafluoropropane,2-(3-amino-4-hydroxy-5-trifluoromethylphenyl)-2-(3-hydroxy-4-amino-5-trifluoromethylphenyl)hexafluoropropane,2-(3-amino-4-hydroxy-5-trifluoromethylphenyl)-2-(3-hydroxy-4-amino-6-trifluoromethylphenyl)hexafluoropropane,2-(3-amino-4-hydroxy-5-trifluoromethylphenyl)-2-(3-hydroxy-4-amino-2-trifluoromethylphenyl)hexafluoropropane,2-(3-amino-4-hydroxy-2-trifluoromethylphenyl)-2-(3-hydroxy-4-amino-5-trifluoromethylphenyl)hexafluoropropane,2-(3-amino-4-hydroxy-6-trifluoromethylphenyl)-2-(3-hydroxy-4-amino-5-trifluoromethylphenyl)hexafluoropropane,and the like, and combinations thereof.

X¹ may be a functional group represented by the following ChemicalFormulae 5 and 6, but is not limited thereto.

In Chemical Formulae 5 and 6,

A¹ is —O—, —CO—, —CR²⁰³R²⁰⁴—, —SO₂—, —S—, or a single bond, wherein R²⁰³and R²⁰⁴ are the same or different and are each independently hydrogenor substituted or unsubstituted alkyl, and in one embodimentfluoroalkyl,

R⁴ to R⁶ are the same or different and are each independently hydrogen,substituted or unsubstituted alkyl, a substituted or unsubstitutedcarboxyl group, a hydroxy group, or a thiol group,

n₃ is an integer ranging from 0 to 2, and

n₄ and n₅ are the same or different and are each independently aninteger ranging from 0 to 3.

In Chemical Formula 2, X² may be the same or different in each repeatingunit, and is each independently a functional group represented by theabove Chemical Formula 3.

In one embodiment, the functional group represented by the aboveChemical Formula 3 may include one selected from functional groupsrepresented by the following Chemical Formulae 7 to 14, or a combinationthereof, but is not limited thereto.

In Chemical Formulae 7 to 14,

R⁷, R⁸ R¹⁰, R¹², R¹⁴, R¹⁶ and R¹⁸ are the same or different in eachrepeating unit and are each independently hydrogen, fluorine, a hydroxygroup, a thiol group, a substituted or unsubstituted C1 to C30 carboxylgroup, or a substituted or unsubstituted C1 to C30 aliphatic organicgroup,

R⁹, R¹¹, R¹³, R¹⁵, R¹⁷, R¹⁹, R²⁰ and R²¹ are the same or different ineach repeating unit and are each independently hydrogen, substituted orunsubstituted C1 to C30 alkyl, a substituted or unsubstituted C1 to C30carboxyl group, a hydroxy group, or a thiol group,

n₉, n₁₁ and n₁₃ are each independently an integer ranging from 0 to 11,and

n₆, n₇, n₈, n₁₀, n₁₂, n₁₄, n₁₅ and n₁₆ are each independently an integerranging from 0 to 3.

In one embodiment, the functional group represented by the aboveChemical Formula 3 may be derived from 1-(3,5-diaminophenyl)-3-octadecylsuccinimide, 4-octadecoxybenzene-1,3-diamine,4-cholesteryloxy-1,3-benzenediamine,4-cyclohexylmethyl-1,3-benzenediamine,4-cyclohexyloxy-1,3-benzenediamine, 4-dodecyloxy-1,3-benzenediamine, ora combination thereof, without limitation.

In Chemical Formulae 1 and 2, Y¹ and Y² are the same or different andare independently an aromatic organic group, a divalent to hexavalentaliphatic organic group, or a divalent to hexavalent alicyclic organicgroup. In one embodiment, Y¹ and Y² are the same or different and areindependently an aromatic organic group, or a divalent to hexavalentalicyclic organic group.

In another embodiment, Y¹ and Y² may be a residual group derived from adicarboxylic acid or a residual group derived from a dicarboxylic acidderivative.

Examples of the dicarboxylic acid include without limitation Y¹(COOH)₂or Y²(COOH)₂ (wherein Y¹ and Y² are the same as Y¹ and Y² of the aboveChemical Formulae 1 and 2).

Examples of the carboxylic acid derivative include without limitationcarbonyl halide derivatives of Y¹(COOH)₂, carbonyl halide derivatives ofY²(COOH)₂, active compounds of an active ester derivative obtained byreacting Y¹(COOH)₂ and 1-hydroxy-1,2,3-benzotriazole, or activecompounds of an active ester derivative obtained by reacting Y²(COOH)₂with 1-hydroxy-1,2,3-benzotriazole (wherein Y¹ and Y² are the same as Y¹and Y² of the above Chemical Formulae 1 and 2).

Examples of the dicarboxylic acid derivative include without limitation4,4′-oxydibenzoylchloride, diphenyloxydicarbonyldichloride,bis(phenylcarbonylchloride)sulfone, bis(phenylcarbonylchloride)ether,bis(phenylcarbonylchloride)phenone, phthaloyldichloride,terephthaloyldichloride, isophthaloyldichloride, dicarbonyldichloride,diphenyloxydicarboxylatedibenzotriazole, and the like, and combinationsthereof.

Y¹ and Y² may include functional groups represented by the followingChemical Formulae 15 to 17, but are not limited thereto.

In Chemical Formulae 15 to 17,

R²² to R²⁵ are the same or different and are each independently hydrogenor substituted or unsubstituted alkyl,

n₁₇ is an integer ranging from 0 to 4,

n₁₈, n₁₉ and n₂₀ are each independently an integer ranging from 0 to 3,and

A² is —O—, —CR²⁰⁵R²⁰⁶—, —CO—, —CONH—, —S—, —SO₂—, or a single bond,wherein R²⁰⁵ and R²⁰⁶ are the same or different and are eachindependently hydrogen or substituted or unsubstituted alkyl, and in oneembodiment fluoroalkyl.

The first polybenzoxazole precursor includes a thermally polymerizablefunctional group at at least one of the terminal end. The thermallypolymerizable functional group binds polymer chains by heat to extend achain length, or is cross-linked with a cross-linking agent to provide ahard film, and therefore the molecular weight of a low molecular weightpolymer can be increased and film properties can be improved.

The thermally polymerizable functional group may be derived from anend-capping monomer. Examples of the end-cappong monomer may includewithout limitation monoamines, monoanhydrides, monocarboxylic acidhalides including a carbon-carbon multiple bond, and the like, andcombinations thereof.

Examples of the monoamines include without limitation toluidine,dimethylaniline, ethylaniline, aminophenol, aminobenzylalcohol,aminoindan, aminoacetonephenone, and the like, and combinations thereof.

Examples of the monoanhydrides include without limitation5-norbornene-2,3-dicarboxylanhydride represented by the followingChemical Formula 18, 3,6-epoxy-1,2,3,6-tetra hydrophthalicanhydriderepresented by the following Chemical Formula 19, isobutenyl succinicanhydride represented by the following Chemical Formula 20, maleicanhydride, aconitic anhydride, 3,4,5,6-tetrahydrophthalic anhydride,cis-1,2,3,6,-tetrahydrophthalic anhydride, itaconic anhydride (IA),citraconic anhydride (CA), 2,3-dimethylmaleic anhydride (DMMA), and thelike, and combinations thereof.

The thermally polymerizable functional group derived from themonoanhydrides can include a functional group represented by thefollowing Chemical Formulae 21 to 25 or a combination thereof, but isnot limited thereto. The thermally polymerizable functional group may becross-linked during heating of the first polybenzoxazole precursorpreparation process, and may be formed as a residual group at theterminal end of the first polybenzoxazole precursor.

In Chemical Formula 21, R²⁶ is —H, —CH₂COOH or —CH₂CHCHCH₃.

In Chemical Formula 22,

R²⁷ and R²⁸ are the same or different and are each independently —H or—CH₃.

In Chemical Formula 24,

R²⁹ is —CH₂— or —O—, and R³⁰ is —H or —CH₃.

In Chemical Formula 25,

R³¹ and R³² are the same or different, and are independently —H, —CH₃ or—OCOCH₃.

The monocarboxylic acid halides including the carbon-carbon multiplebonds may be represented by the following Chemical Formula 26.

In Chemical Formula 26,

R³³ is a substituted or unsubstituted alicyclic organic group or asubstituted or unsubstituted aromatic organic group. The substitutedalicyclic organic group or substituted aromatic organic group issubstituted with a substituent including a substituted or unsubstitutedamidino group, a substituted or unsubstituted alicyclic organic group,or a fused ring of a substituted or unsubstituted alicyclic organicgroup with an aryl group. The substituted alicyclic organic group may bea maleimide group.

Z² is —F, —Cl, —Br, or —I.

Examples of the monocarboxylic acid halides including a carbon-carbonmultiple bond include without limitation 5-norbornene-2-carboxylic acidhalides represented by the following Chemical Formula 27, 4-nadimidobenzoylhalides represented by the following Chemical Formula 28,4-(4-phenylethynylphthimido)benzoylhalides represented by the followingChemical Formula 29, 4-(2-phenylmaleicimido)benzoylhalides representedby the following Chemical Formula 30, benzoylhalides represented by thefollowing Chemical Formula 31, cyclobenzoylhalides represented by thefollowing Chemical Formula 32,4-(3-phenylethynylphthimido)benzoylhalide, 4-maleimido benzoylhalide,and the like, and combinations thereof. These may be used singularly oras a mixture thereof.

In Chemical Formulae 27 to 32,

Z³ to Z⁸ are the same or different and are each independently —F, —Cl,—Br, or —I.

The first polybenzoxazole precursor may include the repeating unitrepresented by above Chemical Formula 1 and the repeating unitrepresented by above Chemical Formula 2 at a mole ratio of about 60:40to about 95:5.

In some embodiments, the first polybenzoxazole precursor may include arepeating unit represented by above Chemical Formula 1 in an amount ofabout 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75,76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93,94, or 95 mole %. Further, according to some embodiments of the presentinvention, the amount of the repeating unit represented by aboveChemical Formula 1 can be in a range from about any of the foregoingamounts to about any other of the foregoing amounts.

In some embodiments, the first polybenzoxazole precursor may include arepeating unit represented by above Chemical Formula 2 in an amount ofabout 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22,23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, or40 mole %. Further, according to some embodiments of the presentinvention, the amount of the repeating unit represented by aboveChemical Formula 2 can be in a range from about any of the foregoingamounts to about any other of the foregoing amounts.

When the first polybenzoxazole precursor includes the repeating unitrepresented by above Chemical Formula 1 and the repeating unitrepresented by above Chemical Formula 2 in an amount within the aboveranges, the dissolution of the positive photosensitive resin compositionin the alkali developing solution may be suppressed in the non-exposedpart. Thereby, the residue ratio and pattern formation properties offilm fabricated by using the positive photosensitive resin compositionmay be effectively improved, and the residue may be effectively removedwithout scum, so the residue removal properties may be effectivelyimproved. In addition, the mechanical properties, the reliability, thesensitivity and the resolution of film fabricated by using the positivephotosensitive resin composition may be also improved.

The first polybenzoxazole precursor may have a weight average molecularweight (Mw) of about 4,000 g/mol to about 20,000 g/mol. When the firstpolybenzoxazole precursor has a weight average molecular weight withinthe above range, the development rate may be effectively controlled, sothe pattern formation properties and the film residue ratiocharacteristics may be improved to provide the enough dissolubility tothe organic solvent. In addition, it may be easily used in the positivephotosensitive resin composition in the various mixing range. In oneembodiment, the first polybenzoxazole precursor may have a weightaverage molecular weight (Mw) of about 5,000 g/mol to about 15,000g/mol.

The polybenzoxazole precursor may further include a secondpolybenzoxazole precursor including a repeating unit represented by thefollowing Chemical Formula 33, and having a thermally polymerizablefunctional group at at least one of the terminal end.

In Chemical Formula 33,

X⁴ is the same or different in each repeating unit and is eachindependently a substituted or unsubstituted C6 to C30 aromatic organicgroup, a substituted or unsubstituted tetravalent to hexavalent C1 toC30 aliphatic organic group, or a substituted or unsubstitutedtetravalent to hexavalent C3 to C30 alicyclic organic group, and

Y⁴ is the same or different in each repeating unit and is eachindependently a substituted or unsubstituted C6 to C30 aromatic organicgroup, a substituted or unsubstituted divalent to hexavalent C1 to C30aliphatic organic group, or a substituted or unsubstituted divalent tohexavalent C3 to C30 alicyclic organic group.

When the polybenzoxazole precursor further includes the secondpolybenzoxazole precursor, the developability in the non-exposed partand exposed part may be effectively controlled to enhance contrastratio.

In Chemical Formula 33, X⁴ is the same or different in each repeatingunit and is each independently aromatic organic group, tetravalent tohexavalent aliphatic organic group, or a tetravalent to hexavalentalicyclic organic group. In one embodiment, X⁴ is the same or differentin each repeating unit and is each independently aromatic organic groupor a tetravalent to hexavalent alicyclic organic group.

In one embodiment, X⁴ may be a residual group derived from aromaticdiamine.

The aromatic diamine is the same as the aromatic diamine in thedescription of X¹ of the above Chemical Formula 1.

X⁴ may be a functional group represented by the above Chemical Formulae5 and 6, but is not limited thereto.

In Chemical Formula 33, Y⁴ is the same or different and is independentlyan aromatic organic group, a divalent to hexavalent aliphatic organicgroup, or a divalent to hexavalent alicyclic organic group. In oneembodiment, Y⁴ is the same or different, and is each independently anaromatic organic group or a divalent to hexavalent alicyclic organicgroup.

In another embodiment, Y⁴ is a residual group derived from dicarboxylicacid or a residual group derived from a dicarboxylic acid derivative.

The dicarboxylic acid may be Y⁴(COOH)₂ (wherein Y⁴ is the same as Y⁴ ofthe above Chemical Formula 33).

Examples of the carboxylic acid derivative may include withoutlimitation carbonyl halide derivatives of Y⁴(COOH)₂, active compounds ofan active ester derivative obtained by reacting Y⁴(COOH)₂ (wherein Y⁴ isthe same as Y⁴ of the above Chemical Formula 33) and1-hydroxy-1,2,3-benzotriazole, and the like, and combinations thereof.

Examples of the dicarboxylic acid derivative are the same as describedabove.

Y⁴ may be a functional group represented by the above Chemical Formulae15 to 17, but is not limited thereto.

The second polybenzoxazole precursor may have a weight average molecularweight (Mw) of about 4,000 g/mol to about 20,000 g/mol. When the secondpolybenzoxazole precursor compound has a weight average molecular weightwithin the above range, the development rate may be effectivelycontrolled to improve the pattern formation properties and the filmresidue ratio characteristics and may be easily used in the positivephotosensitive resin composition in various mixing ranges. In oneembodiment, the second polybenzoxazole precursor may have a weightaverage molecular weight (Mw) of about 5,000 g/mol to about 15,000g/mol.

When the polybenzoxazole precursor includes both of the firstpolybenzoxazole precursor and the second polybenzoxazole precursor, thefirst polybenzoxazole precursor and the second polybenzoxazole precursormay be included at a weight ratio of about 5:95 to about 95:5.

In some embodiments, the polybenzoxazole precursor may include the firstpolybenzoxazole precursor in an amount of about 5, 6, 7, 8, 9, 10, 11,12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29,30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47,48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65,66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83,84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, or 95 weight %. Further,according to some embodiments of the present invention, the amount ofthe first polybenzoxazole precursor can be in a range from about any ofthe foregoing amounts to about any other of the foregoing amounts.

In some embodiments, the polybenzoxazole precursor may include thesecond polybenzoxazole precursor in an amount of about 5, 6, 7, 8, 9,10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27,28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45,46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63,64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81,82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, or 95 weight %.Further, according to some embodiments of the present invention, theamount of the second polybenzoxazole precursor can be in a range fromabout any of the foregoing amounts to about any other of the foregoingamounts.

When the first polybenzoxazole precursor and the second polybenzoxazoleprecursor are included in amounts within the above ranges, thedevelopability may be effectively controlled in the non-exposed part andthe exposed part to improve the sensitivity and the film residue ratiocharacteristics.

(B) Dissolution Controlling Agent

The dissolution controlling agent includes a novolac resin including therepeating unit represented by the above Chemical Formula 4. As usedherein, the novolac resin may be a random copolymer, a block copolymer,or a combination thereof, but is not limited thereto. In one embodiment,the novolac resin can be a random copolymer.

Greater than or equal to about 50 mol % of R³ based on 100 mol % of R³in a repeating unit included in the novolac resin may be present in ameta position with respect to a hydroxy group (OH).

In one embodiment, in the positive photosensitive resin composition,greater than or equal to about 60 mol % of R³ based on 100 mol % of R³in a repeating unit included in the novolac resin may be present in ameta position with respect to a hydroxy group (OH).

In some embodiments, the novolac resin may include a repeating unitrepresented by the above Chemical Formula 3 having R³ present in a metaposition relative to a hydroxy group (OH) in an amount of about 50, 51,52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69,70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87,88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99 or 100 mol %. Further,according to some embodiments of the present invention, the amount ofthe repeating unit having R³ present in a meta position relative to ahydroxy group (OH) can be in a range from about any of the foregoingamounts to about any other of the foregoing amounts.

In exemplary embodiments, in the positive photosensitive resincomposition, greater than or equal to about 90 mol % of R³ based on 100mol % of R³ in a repeating unit included in the novolac resin may bepresent in a meta position and a para position with respect to a hydroxygroup (OH).

In some embodiments, the novolac resin may include a repeating unitrepresented by the above Chemical Formula 3 having R³ present in a metaposition and a para position relative to a hydroxy group (OH) in anamount of about 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, or 100 mol %.Further, according to some embodiments of the present invention, theamount of the repeating unit having R³ present in a meta position and apara position relative to a hydroxy group (OH) can be in a range fromabout any of the foregoing amounts to about any other of the foregoingamounts.

In this case, the repeating unit including R³ present the meta position(R³ _(m)) and the repeating unit including R³ present in the paraposition (R³ _(p)) may be random polymerized or block polymerized, butis not limited thereto. In this case, R³ present the meta position (R³_(m)) may improve the alkali developability and the sensitivity in theexposed part, and R³ present in the para position (R³ _(p)) may suppressthe excessive development in the exposed part and the non-exposed part,so the film residue ratio characteristics may be maintained. Thereby,the alkali developabiity may be effectively controlled when using thepositive photosensitive resin composition, so the sensitivity and thefilm residue ratio characteristics may be improved.

The repeating unit included in the novolac resin may include R³ _(m)present in a metal position and R³ _(p) present in a para position tothe hydroxyl group (OH) in the R³ in a mole ratio of about 5:5 to about10:0.

In some embodiments, the repeating unit included in the novolac resinmay include R³ _(m) present in a meta position to the hydroxyl group(OH) in an amount of about 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60,61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78,79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96,97, 98, 99 or 100 mol %. Further, according to some embodiments of thepresent invention, the amount of R³ _(m) present in a meta position canbe in a range from about any of the foregoing amounts to about any otherof the foregoing amounts.

In some embodiments, the repeating unit included in the novolac resinmay include R³ _(p) present in a para position to the hydroxyl group(OH) in an amount of about zero (a repeating unit represented by theabove Chemical Formula 3 having R³ _(p) is not present), or about 0 (arepeating unit represented by the above Chemical Formula 3 having R³_(p) is present), 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16,17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34,35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, or 50 mol %.Further, according to some embodiments of the present invention, theamount of R³ _(p) present in a para position can be in a range fromabout any of the foregoing amounts to about any other of the foregoingamounts.

In this case, the repeating unit including R³ present the meta position(R³ _(m)) and the repeating unit including R³ present in the paraposition (R³ _(p)) may be random polymerized or block polymerized, butis not limited thereto. When the mole ratio of R³ present the metaposition (R³ _(m)) and R³ present in the para position (R³ _(p)) iswithin the above range, the alkali developabiity may be effectivelycontrolled if using the positive photosensitive resin composition, andthe sensitivity, the film residue ratio characteristics, and the heatresistance may be improved. In one embodiment, the mole ratio of R³present the meta position (R³ _(m)) and R³ present in the para position(R³ _(p)) may range from about 6:4 to about 9:1.

The novolac resin may include a compound including a repeating unitrepresented by the following Chemical Formula 34.

The novolac resin may include the compound including the repeating unitrepresented by the Chemical Formula 4 and the compound including therepeating unit represented by the above Chemical Formula 34 at a weightratio of about 30:70 to about 90:10.

In some embodiments, the novolac resin may include the compoundincluding the repeating unit represented by the Chemical Formula 4 in anamount of about 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43,44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61,62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79,80, 81, 82, 83, 84, 85, 86, 87, 88, 89, or 90 weight %. Further,according to some embodiments of the present invention, the amount ofthe compound including the repeating unit represented by the ChemicalFormula 4 can be in a range from about any of the foregoing amounts toabout any other of the foregoing amounts.

In some embodiments, the novolac resin may include the compoundincluding the repeating unit represented by the Chemical Formula 34 inan amount of about 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22,23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40,41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58,59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, or 70 weight %. Further,according to some embodiments of the present invention, the amount ofthe compound including the repeating unit represented by the ChemicalFormula 34 can be in a range from about any of the foregoing amounts toabout any other of the foregoing amounts.

Alternatively, the novolac resin may include the repeating unitrepresented by the Chemical Formula 4 and the repeating unit representedby the above Chemical Formula 34 at a mole ratio of about 30:70 to about90:10.

In some embodiments, the novolac resin may include the repeating unitrepresented by the Chemical Formula 4 in an amount of about 30, 31, 32,33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50,51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68,69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86,87, 88, 89, or 90 mol %. Further, according to some embodiments of thepresent invention, the amount of the repeating unit represented by theChemical Formula 4 can be in a range from about any of the foregoingamounts to about any other of the foregoing amounts.

In some embodiments, the novolac resin may include the repeating unitrepresented by the Chemical Formula 34 in an amount of about 10, 11, 12,13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30,31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48,49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66,67, 68, 69, or 70 mol %. Further, according to some embodiments of thepresent invention, the amount of the repeating unit represented by theChemical Formula 34 can be in a range from about any of the foregoingamounts to about any other of the foregoing amounts.

When the novolac resin includes the cresol novolac repeating unitrepresented by above Chemical Formula 4 and the phenol novolac repeatingunit represented by above Chemical Formula 34 in an amount within theabove range, the dissolubility to the alkali developing solution may beimproved in the exposed part while maintaining dissolution suppressionin the non-exposed part, so the developability may be effectivelyimproved in the exposed part to improve film residue ratio, sensitivity,and pattern formation properties. In one embodiment, the novolac resinmay include the repeating unit represented by the Chemical Formula 4 andthe repeating unit represented by the above Chemical Formula 34 in amole ratio of about 40:60 to about 80:20.

The novolac resin may have a number average molecular weight (Mn) ofabout 1,000 to about 10,000.

The dissolution controlling agent may further include a phenol compound.

The phenol compound may include compounds represented by the followingChemical Formulae 35 to 41, and combinations thereof, but is not limitedthereto.

In Chemical Formula 35,

R⁴⁶ to R⁵¹ are the same or different and are each independently —H, —OH,substituted or unsubstituted C1 to C10 alkyl, substituted orunsubstituted C1 to C10 alkoxy, or substituted or unsubstituted C1 toC10 alkoxyalkyl, provided that at least one of R⁴⁶ to R⁵¹ is a hydroxygroup, and all of R⁴⁶ to R⁵¹ are not a hydroxy group.

In Chemical Formula 36,

R⁵² to R⁵⁴ are the same or different and are each independently hydrogenor substituted or unsubstituted alkyl,

R⁵⁵ to R⁵⁹ are the same or different and are each independently —H, —OH,or substituted or unsubstituted alkyl, provided that at least one of R⁵⁵to R⁵⁹ is a hydroxy group, and in one embodiment, the alkyl may be —CH₃,and

n₂₇ is an integer ranging from 0 to 5.

In Chemical Formula 37,

R⁶⁰ to R⁶⁵ are the same or different and are each independently —H, —OH,or substituted or unsubstituted alkyl, provided that at least one of R⁶⁰to R⁶⁵ is a hydroxy group,

A⁵ is —CR²⁰⁹R²¹⁰— or a single bond, wherein R²⁰⁹ and R²¹⁰ are the sameor different and are each independently hydrogen or substituted orunsubstituted alkyl, and in one embodiment the alkyl may be —CH₃, and

n₂₈+n₂₉+n₃₀ and n₃₁+n₃₂+n₃₃ are the same or different and are eachindependently an integer of less than or equal to 5.

In Chemical Formula 38,

R⁶⁶ to R⁶⁸ are the same or different and are each independently hydrogenor substituted or unsubstituted alkyl,

n₃₄ and n₃₅ are the same or different and are each independently aninteger ranging from 1 to 5,

n₃₆ and n₃₇ are the same or different and are each independently aninteger ranging from 0 to 4, and

n₃₈ is an integer ranging from 0 to 10.

In Chemical Formula 39,

R⁶⁹ to R⁷⁴ are the same or different and are each independentlyhydrogen, —OH, or substituted or unsubstituted alkyl,

n₃₉ to n₄₂ are the same or different and are each independently aninteger ranging from 1 to 4, and

n₃₉+n₄₁ and n₄₀+n₄₂ are the same or different and are each independentlyan integer of less than or equal to 5.

In Chemical Formula 40,

R⁷⁵ is substituted or unsubstituted alkyl, for example —CH₃,

R⁷⁶ to R⁷⁸ are the same or different and are each independently hydrogenor substituted or unsubstituted alkyl,

n₄₃, n₄₅ and n₄₇ are the same or different and are each independently aninteger ranging from 1 to 5,

n₄₄, n₄₆ and n₄₈ are the same or different, and are each independentlyan integer ranging from 0 to 4, and

n₄₃+n₄₄, n₄₅+n₄₆ and n₄₇+n₄₈ are the same or different and are eachindependently an integer of less than or equal to 5.

In Chemical Formula 41,

R⁷⁹ to R⁸¹ are the same or different and are each independentlysubstituted or unsubstituted alkyl, for example —CH₃,

R⁸² to R⁸⁵ are the same or different and are each independently hydrogenor substituted or unsubstituted alkyl,

n₄₉, n₅₁ and n₅₃ are the same or different and are each independently aninteger ranging from 1 to 5,

n₅₀, n₅₂ and n₅₄ are the same or different and are each independently aninteger ranging from 0 to 4,

n₅₅ is an integer ranging from 1 to 4, and

n₄₉+n₅₀, n₅₁+n₅₂ and n₅₃+n₅₄ are the same or different and are eachindependently an integer of less than or equal to 5.

Examples of the phenol compound may include without limitation3-hydroxy-4-ethylphenol, 2,6-dimethoxymethyl-4-t-butylphenol,2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, and thelike, and combinations thereof.

When the dissolution controlling agent includes the novolac resin andthe phenol compound, the novolac resin and the phenol compound may beincluded at a weight ratio of about 30:5 to about 10:25. In this case,the development sensitivity may not be deteriorated, and the dissolutionspeed of a non-exposed part can be appropriately increased to provide agood pattern, and it is not precipitated when stored in a freezer toprovide excellent storage-stability and to provide high film residueratio and high sensitivity characteristics. In one embodiment, when thedissolution controlling agent includes the novolac resin and the phenolcompound, the novolac resin and the phenol compound may be included at aweight ratio of about 25:10 to about 15:20.

The positive photosensitive resin composition may include thedissolution controlling agent in an amount of about 1 part by weight toabout 30 parts by weight, for example about 1 part by weight to about 20parts by weight, based on about 100 parts by weight of thepolybenzoxazole precursor. In some embodiments, the positivephotosensitive resin composition may include the dissolution controllingagent in an amount of about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13,14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30parts by weight. Further, according to some embodiments of the presentinvention, the amount of dissolution controlling agent can be in a rangefrom about any of the foregoing amounts to about any other of theforegoing amounts.

When the dissolution controlling agent is included in an amount withinthe above range, the non-exposed part can be effectively controlled tobe non-polar, and the exposed part can be effectively controlled to bepolar, so the alkali developability in the exposed part may beeffectively controlled.

(C) Photosensitive Diazoquinone Compound

The photosensitive diazoquinone compound may be a compound including a1,2-benzoquinone diazide or 1,2-naphtoquinone diazide structure.

The photosensitive diazoquinone compound may include the compoundsrepresented by the following Chemical Formulae 42, and 44 to 46, andcombinations thereof, but is not limited thereto.

In Chemical Formula 42,

R⁸⁶ to R⁸⁸ are the same or different and are each independently hydrogenor substituted or unsubstituted C1 to C30 alkyl, for example CH₃.

R⁸⁹ to R⁹¹ are the same or different and are each independently —OQ,wherein Q is hydrogen, a functional group represented by the followingChemical Formula 43a, or a functional group represented by the followingChemical Formula 43b, provided that all of the Qs are not simultaneouslyhydrogen. In one embodiment, Q is hydrogen or a functional grouprepresented by the above Chemical Formula 43a.

When Q is a functional group represented by the following ChemicalFormula 43a, the photosensitive diazoquinone compound can havephotosensitivity with respect to light having a wide range of wavelengthincluding i-line (about 365 nm), h-line (about 405 nm), and g-line(about 436 nm) and thus may be easily used for fabrication of an organiclight emitting display device (OLED).

On the other hand, when Q is a functional group represented by thefollowing Chemical Formula 43b, the photosensitive diazoquinone compoundcan have photosensitivity with respect to light of i-line (about 365nm), and thus may be easily used for fabrication of a semiconductordevice.

n₅₆ to n₅₈ are each independently an integer ranging from 1 to 3.

In Chemical Formula 44,

R⁹² is hydrogen or substituted or unsubstituted C1 to C30 alkyl,

R⁹³ to R⁹⁵ are the same or different and are each independently —OQ,wherein Q is the same as defined in the above Chemical Formula 42, and

n₅₉ to n₆₁ are each independently an integer ranging from 1 to 3.

In Chemical Formula 45,

A⁶ is —CO— or wherein R²¹¹ and R²¹² are the same or different and areeach independently substituted or unsubstituted C1 to C30 alkyl,

R⁹⁶ to R⁹⁹ are the same or different and are each independentlyhydrogen, substituted or unsubstituted C1 to C30 alkyl, —OQ or —NHQ,wherein Q is the same as defined in the above Chemical Formula 42,

n₆₂ to n₆₅ are each independently an integer ranging from 1 to 4,

n₆₂+n₆₃ and n₆₄+n₆₅ are each independently an integer of less than orequal to 5, and

at least one of R⁹⁶ and R⁹⁷ is —OQ, and one aromatic ring includes oneto three OQs and the other aromatic ring includes one to four OQs.

In Chemical Formula 46,

R¹⁰⁰ to R¹⁰⁷ are the same or different and are each independentlyhydrogen or substituted or unsubstituted C1 to C30 alkyl,

n₆₆ and n₆₇ are each independently an integer ranging from 1 to 5, and

Q is the same as defined in the above Chemical Formula 42.

The positive photosensitive resin composition may include thephotosensitive diazoquinone compound in an amount of about 5 parts byweight to about 100 parts by weight, based on about 100 parts by weightof the polybenzoxazole precursor (A). In some embodiments, the positivephotosensitive resin composition may include the photosensitivediazoquinone compound in an amount of about 5, 6, 7, 8, 9, 10, 11, 12,13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30,31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48,49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66,67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84,85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, or 100 partsby weight. Further, according to some embodiments of the presentinvention, the amount of the photosensitive diazoquinone compound can bein a range from about any of the foregoing amounts to about any other ofthe foregoing amounts.

When the amount of the photosensitive diazoquinone compound is withinthe above range, the pattern can be well-formed without a residue fromexposure, and film thickness loss during development can be preventedand thereby a good pattern can be provided.

(D) Silane Compound

The silane compound can improve adherence between the photosensitiveresin composition and a substrate.

Examples of the silane compound may include without limitation compoundsrepresented by the following Chemical Formulae 47 to 49; or a silanecompound having a carbon-carbon unsaturated bond such asvinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane,vinyltris(β-methoxyethoxy)silane, 3-methacryloxypropyltrimethoxysilane,3-acryloxypropyltrimethoxysilane, p-styryltrimethoxysilane,3-methacryloxypropylmethyldimethoxysilane,3-methacryloxypropylmethyldiethoxysilane,trimethoxy[3-(phenylamino)propyl]silane, and the like, and combinationsthereof.

In Chemical Formula 47,

R¹⁰⁸ is a vinyl group, substituted or unsubstituted alkyl, orsubstituted or unsubstituted aryl, for example 3-(meth)acryloxypropyl,p-styryl, or 3-(phenylamino)propyl,

R¹⁰⁹ to R¹¹¹ are the same or different and are each independentlysubstituted or unsubstituted alkoxy, substituted or unsubstituted alkyl,or halogen, wherein at least one of R¹⁰⁹ to R¹¹¹ is alkoxy or halogen,and in one embodiment, the alkoxy may be C1 to C8 alkoxy, and the alkylmay be C1 to C20 alkyl.

In Chemical Formula 48,

R¹¹² is —NH₂ or —NHCOCH₃,

R¹¹³ to R¹¹⁵ are the same or different and are each independentlysubstituted or unsubstituted alkoxy, and in one embodiment, the alkoxyis —OCH₃ or —OCH₂CH₃, and

n₆₈ is an integer ranging from 1 to 5.

In Chemical Formula 49,

R¹¹⁶ to R¹¹⁹ are the same or different and are each independentlysubstituted or unsubstituted alkyl or substituted or unsubstitutedalkoxy, for example —CH₃ or —OCH₃,

R¹²⁰ and R¹²¹ are the same or different and are each independentlysubstituted or unsubstituted amino, for example —NH₂ or —NHCOCH₃, and

n₆₉ and n₇₀ are the same or different and are each independently aninteger ranging from 1 to 5.

The positive photosensitive resin composition may include the silanecompound in an amount of about 0.1 parts by weight to about 30 parts byweight based on about 100 parts by weight of the polybenzoxazoleprecursor. In some embodiments, the positive photosensitive resincomposition may include the silane compound in an amount of about 0.1,0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10,11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28,29, or 30 parts by weight. Further, according to some embodiments of thepresent invention, the amount of the silane compound can be in a rangefrom about any of the foregoing amounts to about any other of theforegoing amounts.

When the silane compound is included in an amount within the aboverange, adherence between lower and upper layers can be sufficientlyimproved, a residual film may not remain after development, and opticalproperties (transmittance) and mechanical properties such as tensilestrength, elongation, and the like may be improved.

(E) Acid Generator

Examples of the acid generator may include without limitationsulfonate-based acid generators such as paratoluene sulfonate, and thelike, sulfonic acid-based acid generators such as methane sulfonic acid,and the like, and combinations thereof.

In one embodiment, the acid generator may include sulfonates such aspyridinium paratoluene sulfonate, propargyl paratoluene sulfonate,S-(2-naphthalenecarbonyl methyltetrahydrothiophenium trifluoromethanesulfonenate), triphenylsulfonium triflate,(4-methoxythiophenyl)methylphenyl sulfonium triflate,(4-methylphenyl)diphenyl sulfonium triflate, dimethylphenyl sulfoniumnonafluorobutane sulfonate, dimethylphenyl sulfonium trifluoromethanesulfonate, 2-methoxyethyl paratoluene sulfonate, butyl paratoluenesulfonate, and the like, arylsulfonic acids such as p-toluene sulfonicacid, benzene sulfonic acid, and the like, trifluoromethane sulfonicacid, trifluorobutane sulfonic acid, and the like, alkylsulfonic acidssuch as perfluoroalkyl sulfonic acid, methane sulfonic acid, ethanesulfonic acid, butane sulfonic acid, and the like, and combinationsthereof, but is not limited thereto.

The acid generator is a catalyst for a dehydration reaction of thehydroxyl group-containing polyamide of the polybenzoxazole precursor andcyclization reaction, and thus a cyclization reaction can be performedsmoothly even if curing temperature is decreased.

The positive photosensitive resin composition may include the acidgenerator in an amount of about 0.1 to about 20 parts by weight, forexample about 0.5 to about 10 parts by weight, and as another exampleabout 1 to about 8 parts by weight, based on about 100 parts by weightof the polybenzoxazole precursor. In some embodiments, the positivephotosensitive resin composition may include the acid generator in anamount of about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4,5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 parts byweight. Further, according to some embodiments of the present invention,the amount of the acid generator can be in a range from about any of theforegoing amounts to about any other of the foregoing amounts.

When the acid generator is included in an amount within the above range,the polybenzoxazole precursor may be effectively cyclized and curedenough to improve the film properties. The alkali developability in theexposed part may be improved during the exposition to effectively carryout the patterning.

(F) Solvent

The solvent may be an organic solvent. Examples of the organic solventmay include without limitation N-methyl-2-pyrrolidone, γ-butyrolactone,N,N-dimethylacetamide, dimethylsulfoxide, diethylene glycoldimethylether, diethylene glycol diethylether, diethylene glycoldibutylether, propyleneglycol monomethylether, dipropylene glycolmonomethylether, propylene glycol monomethylether acetate, methyllactate, ethyl lactate, butyl lactate, methyl-1,3-butylene glycolacetate, 1,3-butylene glycol-3-monomethylether, methyl pyruvate, ethylpyruvate, methyl-3-methoxy propionate, and the like, and combinationsthereof. The solvent may be used singularly or as a mixture of two ormore.

In one embodiment, the solvent may be a mixed solvent ofγ-butyrolactone, ethyl lactate, and propylene glycol monomethylether. Asused herein, ethyl lactate may be present in an amount of about 25 toabout 60 parts by weight and propylene glycol monomethylether may bepresent in an amount of about 10 to about 40 parts by weight based on100 parts by weight of γ-butyrolactone.

The positive photosensitive resin composition may include the solvent inan amount of about 50 parts by weight to about 900 parts by weight, forexample about 50 parts by weight to about 600 parts by weight, based onabout 100 parts by weight of the polybenzoxazole precursor. When thesolvent is used in an amount within the above range, a sufficientlythick film may be obtained, and good solubility and coating can beprovided.

(G) Other Additive(s)

The positive photosensitive resin composition according to oneembodiment further include (G) one or more other additives.

Non-limiting examples of the additive include suitable surfactantsand/or leveling agents, which may be used in order to prevent a stain ofthe film or to improve development.

Other non-limiting examples of additives may include fluorine-basedadditives and/or siloxane-based additives.

The process for forming a pattern using a positive photosensitive resincomposition may include: coating a positive photosensitive resincomposition on a supporting substrate using spin coating, slit coating,inkjet printing, and the like; drying the coated positive photosensitiveresin composition to provide a positive photosensitive resin compositionlayer; exposing the positive photosensitive resin composition layer;developing the positive photosensitive resin composition layer using analkali aqueous solution to provide a photosensitive resin film; andheating the photosensitive resin film. The conditions of processes toprovide a pattern are widely known in this art, so detailed descriptionsthereof will be omitted in this specification.

According to another embodiment of the present invention, aphotosensitive resin film fabricated using the positive photosensitiveresin composition is provided. The photosensitive resin film may be aninsulation layer, a buffer layer, or a protective layer.

The photosensitive resin film may have sensitivity of about 100 to about150 mJ/cm². Within this range, sensitivity may be increased to improve ayield and reduce a time during processes. In one embodiment, thephotosensitive resin film may have sensitivity of about 110 to about 150mJ/cm².

According to yet another embodiment of the present invention, asemiconductor device including the photosensitive resin film isprovided. The semiconductor device may be an organic light emittingdiode (OLED) or a liquid crystal display (LCD).

EXAMPLE

The following examples illustrate the present invention in more detail.However, it is understood that the present invention is not limited bythese examples.

Synthesis Example 1 Synthesis of Polybenzoxazole Precursor (PBO-1)

17.4 g of2,2-bis(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3,-hexafluoropropane is putin a four-necked flask mounted with an agitator, a temperaturecontrolling device, a nitrogen gas injector, and a cooler while nitrogenis passed therethrough, and 280 g of N-methyl-2-pyrrolidone (NMP) isadded thereto.

When the solid is completely dissolved, as a catalyst, 9.9 g of pyridineis added thereto. The resultant mixture is maintained at a temperatureranging from 0° C. to 5° C., and a solution prepared by dissolving 13.3g of 4,4′-oxydibenzoylchloride in 142 g of N-methyl-2-pyrrolidone (NMP)is slowly added thereto in a dropwise fashion for 30 minutes. Theresulting mixture is reacted for one hour at a temperature ranging from0° C. to 5° C. and then, heated up to room temperature and reacted for 1hour. Then, 1.6 g of 5-norbornene-2,3-dicarboxylanhydride is addedthereto. The mixture is agitated at room temperature for 2 hours tocomplete the reaction. The resultant reaction mixture is added to amixed solution of water/methanol (volume ratio=10/1) to produce aprecipitate. The precipitate is filtered, sufficiently cleansed withwater, vacuum-dried at 80° C. for more than 24 hours, preparing apolybenzoxazole precursor (PBO-1). The polybenzoxazole precursor (PBO-1)has a weight average molecular weight of 9,800 g/mol.

Synthesis Example 2 Synthesis of Polybenzoxazole Precursor (PBO-2)

23.1 g of2,2-bis(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3,-hexafluoropropane and 12.4g of 1-(3,5-diaminophenyl)-3-octadecyl succinimide are put in afour-necked flask mounted with an agitator, a temperature controllingdevice, a nitrogen gas injector, and a cooler while nitrogen is passedtherethrough, and 200 g of N-methyl-2-pyrrolidone (NMP) is addedthereto.

When the solid is completely dissolved, as a catalyst, 12.8 g ofpyridine is added thereto. The resultant mixture is maintained at atemperature ranging from 0° C. to 5° C., and a solution prepared bydissolving 23.1 g of 4,4′-oxydibenzoylchloride in 131 g ofN-methyl-2-pyrrolidone (NMP) is slowly added thereto in a dropwisefashion for 30 minutes. The resulting mixture is reacted for one hour ata temperature ranging from 0° C. to 5° C. and then, heated up to roomtemperature and reacted for 1 hour. Then, 4.0 g of5-norbornene-2,3-dicarboxylanhydride is added thereto. The mixture isagitated at room temperature for 2 hours to complete a reaction. Theresultant reaction mixture is added to a mixed solution ofwater/methanol (volume ratio=10/1) to produce a precipitate. Theprecipitate is filtered, sufficiently cleansed with water, vacuum-driedat 80° C. for more than 24 hours, preparing a polybenzoxazole precursor(PBO-1). The polybenzoxazole precursor (PBO-2) has a weight averagemolecular weight of 9,500 g/mol.

Synthesis Example 3 Synthesis of Polybenzoxazole Precursor (PBO-3)

20.5 g of2,2-bis(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3,-hexafluoropropane and 9.1g of 4-octadecoxybenzene-1,3-diamine are put in a four-necked flaskmounted with an agitator, a temperature controlling device, a nitrogengas injector, and a cooler while nitrogen is passed therethrough, and232 g of N-methyl-2-pyrrolidone (NMP) is added thereto.

When the solid is completely dissolved, as a catalyst, 11.4 g ofpyridine is added thereto. The resultant mixture is maintained at atemperature ranging from 0° C. to 5° C., and a solution prepared bydissolving 20.5 g of 4,4′-oxydibenzoylchloride in 117 g ofN-methyl-2-pyrrolidone (NMP) is slowly added thereto in a dropwisefashion for 30 minutes. The resulting mixture is reacted for one hour ata temperature ranging from 0° C. to 5° C. and then, heated up to roomtemperature and reacted for 1 hour. Then, 3.5 g of5-norbornene-2,3-dicarboxylanhydride is added thereto. The mixture isagitated at room temperature for 2 hours to complete a reaction. Theresultant reaction mixture is added to a mixed solution ofwater/methanol (volume ratio=10/1) to produce a precipitate. Theprecipitate is filtered, sufficiently cleansed with water, vacuum-driedat 80° C. for more than 24 hours, preparing a polybenzoxazole precursor(PBO-3). The polybenzoxazole precursor (PBO-3) has a weight averagemolecular weight of 9,200 g/mol.

Example 1 Preparation of Positive Photosensitive Resin Composition

4.05 g of the polybenzoxazole precursor (PBO-1) according to SynthesisExample 1 and 0.45 g of polybenzoxazole precursor (PBO-2) according toSynthesis Example 2 are dissolved in 25 g of a mixed solvent ofγ-butyrolactone (GBL)/ethyl lactate (EL)/propylene glycolmonomethylether (PGME) (weight ratio=5/3/2). 1 g of the photosensitivediazoquinone compound represented by the following Chemical Formula 50,0.2 g of trimethoxy[3-(phenylamino)propyl]silane represented by thefollowing Chemical Formula 51 as a silane compound, 0.2 g of thecompound represented by the following Chemical Formula 52 as adissolution controlling agent, and 0.2 g of the compound represented bythe following Chemical Formula 53, including a meta cresol novolacrepeating unit and a para cresol novolac repeating unit at a ratio of6:4, and having a number average molecular weight of 4,000, and 0.1 g ofpropargyl paratoluene sulfonate represented by the following ChemicalFormula 54 as acid generator are added and dissolved therein. Thesolution is filtered with a 0.45 μm fluorine resin filter, to prepare apositive photosensitive resin composition.

In Chemical Formula 50,

Q is the same as defined in the above Chemical Formula 42, and 67% of Qis substituted with the above Chemical Formula 43a.

Example 2 Preparation of Positive Photosensitive Resin Composition

3.6 g of the polybenzoxazole precursor (PBO-1) according to SynthesisExample 1 and 0.9 g of polybenzoxazole precursor (PBO-2) according toSynthesis Example 2 are dissolved in 25 g of a mixed solvent ofγ-butyrolactone (GBL)/ethyl lactate (EL)/propylene glycolmonomethylether (PGME) (weight ratio=5/3/2). 1 g of the photosensitivediazoquinone compound represented by Chemical Formula 50, 0.2 g oftrimethoxy[3-(phenylamino)propyl]silane represented by Chemical Formula51 as a silane compound, 0.2 g of the compound represented by ChemicalFormula 52 as a dissolution controlling agent, and 0.2 g of the compoundrepresented by Chemical Formula 53, including a meta cresol novolacrepeating unit and a para cresol novolac repeating unit at a ratio of6:4, and having a number average molecular weight of 4,000, and 0.1 g ofpropargyl paratoluene sulfonate represented by Chemical Formula 54 asacid generator are added and dissolved therein. The solution is filteredwith a 0.45 μm fluorine resin filter, to prepare a positivephotosensitive resin composition.

Example 3 Preparation of Positive Photosensitive Resin Composition

3.15 g of the polybenzoxazole precursor (PBO-1) according to SynthesisExample 1 and 1.35 g of polybenzoxazole precursor (PBO-2) according toSynthesis Example 2 are dissolved in 25 g of a mixed solvent ofγ-butyrolactone (GBL)/ethyl lactate (EL)/propylene glycolmonomethylether (PGME) (weight ratio=5/3/2). 1 g of the photosensitivediazoquinone compound represented by Chemical Formula 50, 0.2 g oftrimethoxy[3-(phenylamino)propyl]silane represented by Chemical Formula51 as a silane compound, 0.2 g of the compound represented by ChemicalFormula 52 as a dissolution controlling agent, and 0.2 g of the compoundrepresented by Chemical Formula 53, including a meta cresol novolacrepeating unit and a para cresol novolac repeating unit at a ratio of6:4, and having a number average molecular weight of 4,000, and 0.1 g ofpropargyl paratoluene sulfonate represented by Chemical Formula 54 asacid generator are added and dissolved therein. The solution is filteredwith a 0.45 μm fluorine resin filter, to prepare a positivephotosensitive resin composition.

Example 4 Preparation of Positive Photosensitive Resin Composition

A positive photosensitive resin composition is prepared according to thesame method as in Example 1 except for using the polybenzoxazoleprecursor (PBO-3) according to Synthesis Example 3 instead of thepolybenzoxazole precursor (PBO-2) according to Synthesis Example 2.

Example 5 Preparation of Positive Photosensitive Resin Composition

A positive photosensitive resin composition is prepared according to thesame method as in Example 2 except for using the polybenzoxazoleprecursor (PBO-3) according to Synthesis Example 3 instead of thepolybenzoxazole precursor (PBO-2) according to Synthesis Example 2.

Example 6 Preparation of Positive Photosensitive Resin Composition

A positive photosensitive resin composition is prepared according to thesame method as in Example 3 except for using the polybenzoxazoleprecursor (PBO-3) according to Synthesis Example 3 instead of thepolybenzoxazole precursor (PBO-2) according to Synthesis Example 2.

Comparative Example 1 Preparation of Positive Photosensitive ResinComposition

4.5 g of polybenzoxazole precursor (PBO-1) according to SynthesisExample 1 is dissolved in 25 g of a mixed solvent of γ-butyrolactone(GBL)/ethyl lactate (EL)/propylene glycol monomethylether (PGME) (weightratio=5/3/2). 1 g of the photosensitive diazoquinone compoundrepresented by Chemical Formula 50, 0.2 g oftrimethoxy[3-(phenylamino)propyl]silane represented by Chemical Formula51 as a silane compound, 0.2 g of the compound represented by ChemicalFormula 52 as a dissolution controlling agent, and 0.2 g of the compoundrepresented by Chemical Formula 53, including a meta cresol novolacrepeating unit and a para cresol novolac repeating unit at a ratio of6:4, and having a number average molecular weight of 4,000, and 0.1 g ofpropargyl paratoluene sulfonate represented by Chemical Formula 54 asacid generator are added and dissolved therein. The solution is filteredwith a 0.45 μm fluorine resin filter, to prepare a positivephotosensitive resin composition.

Comparative Example 2 Preparation of Positive Photosensitive ResinComposition

4.5 g of polybenzoxazole precursor (PBO-1) according to SynthesisExample 1 is dissolved in 25 g of a mixed solvent of γ-butyrolactone(GBL)/ethyl lactate (EL)/propylene glycol monomethylether (PGME) (weightratio=5/3/2). 1.7 g of the photosensitive diazoquinone compoundrepresented by the above Chemical Formula 50, 0.2 g oftrimethoxy[3-(phenylamino)propyl]silane represented by Chemical Formula51 as a silane compound, 0.2 g of the compound represented by ChemicalFormula 52 as a dissolution controlling agent, and 0.2 g of the compoundrepresented by Chemical Formula 53, including a meta cresol novolacrepeating unit and a para cresol novolac repeating unit at a ratio of6:4, and having a number average molecular weight of 4,000, and 0.1 g ofpropargyl paratoluene sulfonate represented by Chemical Formula 54 asacid generator are added and dissolved therein. The solution is filteredwith a 0.45 μm fluorine resin filter, to prepare a positivephotosensitive resin composition.

Comparative Example 3 Preparation of Positive Photosensitive ResinComposition

4.5 g of polybenzoxazole precursor (PBO-1) according to SynthesisExample 1 is dissolved in 25 g of a mixed solvent of γ-butyrolactone(GBL)/ethyl lactate (EL)/propylene glycol monomethylether (PGME) (weightratio=5/3/2). 1.7 g of the photosensitive diazoquinone compoundrepresented by the above Chemical Formula 50, 0.2 g oftrimethoxy[3-(phenylamino)propyl]silane represented by Chemical Formula51 as a silane compound, 0.2 g of the compound represented by ChemicalFormula 52 as a dissolution controlling agent, 1.0 g of the compoundrepresented by Chemical Formula 53, including a meta cresol novolacrepeating unit and a para cresol novolac repeating unit at a ratio of6:4, and having a number average molecular weight of 4,000, and 0.1 g ofpropargyl paratoluene sulfonate represented by Chemical Formula 54 asacid generator are added and dissolved therein. The solution is filteredwith a 0.45 μm fluorine resin filter, to prepare a positivephotosensitive resin composition.

Comparative Example 4 Preparation of Positive Photosensitive ResinComposition

4.5 g of polybenzoxazole precursor (PBO-1) according to SynthesisExample 1 is dissolved in 25 g of a mixed solvent of γ-butyrolactone(GBL)/ethyl lactate (EL)/propylene glycol monomethylether (PGME) (weightratio=5/3/2), 1 g of the photosensitive diazoquinone compoundrepresented by Chemical Formula 50, 0.2 g oftrimethoxy[3-(phenylamino)propyl]silane represented by Chemical Formula51 as a silane compound, 0.2 g of the compound represented by ChemicalFormula 52 as a dissolution controlling agent, 0.2 g of the compoundrepresented by Chemical Formula 53, including a meta cresol novolacrepeating unit and a para cresol novolac repeating unit at a ratio of2:8, and having a number average molecular weight of 4,000, and 0.1 g ofpropargyl paratoluene sulfonate represented by Chemical Formula 54 asacid generator are added and dissolved therein. The solution is filteredwith a 0.45 μm fluorine resin filter, to prepare a positivephotosensitive resin composition.

Comparative Example 5 Preparation of Positive Photosensitive ResinComposition

4.05 g g of the polybenzoxazole precursor (PBO-1) according to SynthesisExample 1 and 0.45 g of polybenzoxazole precursor (PBO-2) according toSynthesis Example 2 are dissolved in 25 g of a mixed solvent ofγ-butyrolactone (GBL)/ethyl lactate (EL)/propylene glycolmonomethylether (PGME) (weight ratio=5/3/2). 1 g of the photosensitivediazoquinone compound represented by Chemical Formula 50, 0.2 g oftrimethoxy[3-(phenylamino)propyl]silane represented by Chemical Formula51 as a silane compound, 0.2 g of the compound represented by ChemicalFormula 52 as a dissolution controlling agent, and 0.2 g of the compoundrepresented by the above Chemical Formula 53, including a meta cresolnovolac repeating unit and a para cresol novolac repeating unit at aratio of 2:8, and having a number average molecular weight of 4,000, and0.1 g of propargyl paratoluene sulfonate represented by Chemical Formula54 as acid generator are added and dissolved therein. The solution isfiltered with a 0.45 μm fluorine resin filter, to prepare a positivephotosensitive resin composition.

Experimental Example 1 Evaluation for Sensitivity, Resolution, FilmResidue Ratio, and Scum Generation

The positive photosensitive resin compositions according to Examples 1to 6 and Comparative Examples 1 to 5 are coated on a 8 inch wafer byusing a spin coater (1H-DX2) made by MIKASA Co., Ltd. and then, heatedon a hot plate at 120° C. for 120 seconds, forming 4.15 μm-thickpolybenzoxazole precursor films.

The photosensitive polybenzoxazole precursor films are sequentiallyexposed through a mask having various patterns by an I-line stepper (NSRi10C) manufactured by Japan Nikon from 25 mJ/cm² to 400 mJ/cm² at aninterval of 5 mJ/cm², dissolved in a 2.38 wt % tetramethyl ammoniumhydroxide (TMAH) aqueous solution at room temperature for 60 seconds (2puddles) to remove the exposed part, and washed with pure water for 30seconds. Then, the obtained patterns are cured in an oven to cure at250° C. for 60 minutes, to provide patterned films.

In order to measure sensitivity, the optimal exposure time is determinedwhen a 10 μm L/S (line and space) pattern is formed in a line width of 1to 1 after exposure and development, and the resolution is determined asthe minimum pattern size at the optimal exposure time. The resolution isobserved through an optical microscope. The results are shown in thefollowing Table 1.

Because a decrease in the film thickness can affect development and theresulting film thickness, it is preferable that the film thickness isless decreased during development. In order to measure this, thepre-baked film is immersed in a 2.38 wt % tetramethyl ammonium hydroxide(TMAH) aqueous solution for different times and washed with water, sothe change of film thickness is measured to calculate the residual filmratio (thickness after development/thickness before development, unit:%). The results are shown in the following Table 2. The film thicknesschange after pre-baking, development, and curing is measured by usingST4000-DLX equipment manufactured by KMAC Co.

In addition, in order to check the scum generation, the patterned shapeis observed by KLA Tencor 8100XP (manufactured by KLA Instruments)CD-SEM (critical dimension scanning electron microscope) equipment andwhether residues exist in either the wall surface or the bottom isdetermined. The results are shown in the following Table 1.

<Evaluation Reference of Scum>

None: no residue on the bottom

Yes: residues on the bottom

TABLE 1 Film thickness (μm) Film After residue Pre- devel- ratioSensitivity Resolution baking opment (%) (mJ/cm²) (μm) Scum Example 14.17 3.81 91 150 3 None Example 2 4.10 3.66 89 125 2 None Example 3 4.153.55 86 115 2 None Example 4 4.12 3.70 90 135 3 None Example 5 4.15 3.6989 130 2 None Example 6 4.17 3.59 86 110 2 None Comparative 4.11 3.07 75160 3 None Example 1 Comparative 4.15 3.71 89 285 5 Yes Example 2Comparative 4.12 3.50 85 220 4 Yes Example 3 Comparative 4.10 2.67 65160 3 None Example 4 Comparative 4.15 2.93 71 180 3 Yes Example 5

As shown in Table 1, the positive photosensitive resin compositionsaccording to Examples 1 to 6 including the polybenzoxazole precursorprepared by using hydrophobic diamine and the dissolution controllingagent including a novolac resin having a predetermined structure exhibitan excellent film residue ratio greater than or equal to 86%; scum isnot found; and the sensitivity and the resolution are excellent.

On the other hand, the positive photosensitive resin compositionsaccording to comparative Examples 1 to 4 including no polybenzoxazoleprecursor prepared by using hydrophobic diamine exhibit deterioratedsensitivity. The positive photosensitive resin compositions according toComparative Examples 1, 3 and 4 exhibit deteriorated film residue ratio;and the positive photosensitive resin compositions according toComparative Examples 2 and 3 exhibited deteriorated resolution andgenerated scum.

Particularly, in Comparative Example 2, the amount of a photosensitivediazoquinone compound for suppressing the dissolution to the alkalideveloping solution is increased in order to improve the film residueratio which deteriorated in Comparative Example 1. However, although thefilm residue ratio is improved compared to Comparative Example 1,Comparative Example 2 exhibited deteriorated sensitivity and resolutionand generated scum.

Comparative Example 3 include more of the dissolution controlling agentfor accelerating the dissolution to the alkali developing solution inorder to improve sensitivity and resolution compared to ComparativeExample 2. However, Comparative Example 3 exhibited deteriorated filmresidue ratio and still generated scum although the sensitivity and theresolution are improved compared to Comparative Example 2.

In addition, Comparative Examples 4 and 5 include the compound having aratio of the meta cresol novolac repeating unit and the para cresolnovolac repeating unit of about 2:8 and the number average molecularweight of about 4,000 in order to improve the sensitivity compared toComparative Examples 2 and 3. However, Comparative Examples 4 and 5exhibit significantly deteriorated film residue ratio althoughsensitivity is improved compared to Comparative Examples 2 and 3. WhileComparative Example 4 did not generated scum, Comparative Example 5still generated scum.

Many modifications and other embodiments of the invention will come tomind to one skilled in the art to which this invention pertains havingthe benefit of the teachings presented in the foregoing descriptions.Therefore, it is to be understood that the invention is not to belimited to the specific embodiments disclosed and that modifications andother embodiments are intended to be included within the scope of theappended claims. Although specific terms are employed herein, they areused in a generic and descriptive sense only and not for purposes oflimitation, the scope of the invention being defined in the claims.

What is claimed is:
 1. A positive photosensitive resin composition,comprising (A) a polybenzoxazole precursor including a firstpolybenzoxazole precursor including a repeating unit represented by thefollowing Chemical Formula 1 and a repeating unit represented by thefollowing Chemical Formula 2, and having a thermally polymerizablefunctional group at at least one of the terminal end; (B) a dissolutioncontrolling agent including a novolac resin including a repeating unitrepresented by the following Chemical Formula 4; (C) a photosensitivediazoquinone compound; (D) a silane compound; (E) an acid generator; and(F) a solvent:

wherein, in Chemical Formulae 1 and 2, X¹ is the same or different ineach repeating unit and is each independently a substituted orunsubstituted C6 to C30 aromatic organic group, a substituted orunsubstituted tetravalent to hexavalent C1 to C30 aliphatic organicgroup, or a substituted or unsubstituted tetravalent to hexavalent C3 toC30 alicyclic organic group, X² is the same or different in eachrepeating unit, and is independently a functional group represented bythe following Chemical Formula 3, and Y¹ and Y² are the same ordifferent and are each independently a substituted or unsubstituted C6to C30 aromatic organic group, a substituted or unsubstituted divalentto hexavalent C1 to C30 aliphatic organic group, or substituted orunsubstituted divalent to hexavalent C3 to C30 alicyclic organic group,

wherein, in Chemical Formula 3, Z¹ is the same or different in eachrepeating unit and is each independently a single bond, —O—, —COO—,—OCO—, —NH—, —CONH—, substituted or unsubstituted C1 to C15 alkylene,substituted or unsubstituted C2 to C15 alkenylene, or substituted orunsubstituted C2 to C15 alkynylene, G¹ is the same or different in eachrepeating unit and is each independently a single bond, a substituted orunsubstituted C6 to C30 aromatic organic group, a substituted orunsubstituted divalent to hexavalent C3 to C30 alicyclic organic group,or a substituted or unsubstituted divalent to hexavalent C2 to C30heterocyclic group, R¹ is the same or different in each repeating unitand is each independently hydrogen, fluorine, a hydroxy group, a thiolgroup, a substituted or unsubstituted C1 to C30 carboxyl group, or asubstituted or unsubstituted C1 to C30 aliphatic organic group, each R²is the same or different in each repeating unit and is eachindependently hydrogen, substituted or unsubstituted C1 to C30 alkyl, asubstituted or unsubstituted C1 to C30 carboxyl group, a hydroxy group,or a thiol group, n1 is an integer ranging from 1 to 5, and n2 is aninteger ranging from 0 to 3,

wherein, in Chemical Formula 4, R³ is the same or different in eachrepeating unit and is each independently a substituted or unsubstitutedC1 to C20 aliphatic organic group, wherein greater than or equal toabout 50 mol % of R³ based on 100 mol % of R³ in a repeating unitincluded in the novolac resin is present in a meta position with respectto a hydroxy group (OH).
 2. A positive photosensitive resin compositioncomprising: (A) a polybenzoxazole precursor including a firstpolybenzoxazole precursor including a repeating unit represented by thefollowing Chemical Formula 1 and a repeating unit represented by thefollowing Chemical Formula 2, and having a thermally polymerizablefunctional group at at least one of the terminal end:

wherein, in Chemical Formulae 1 and 2, X¹ is the same or different ineach repeating unit and is each independently a substituted orunsubstituted C6 to C30 aromatic organic group, a substituted orunsubstituted tetravalent to hexavalent C1 to C30 aliphatic organicgroup, or a substituted or unsubstituted tetravalent to hexavalent C3 toC30 alicyclic organic group, X² is the same or different in eachrepeating unit and is independently a functional group represented byrepresented by the following Chemical Formulae 7 to 14, or a combinationthereof:

wherein, in Chemical Formulae 7 to 14, R⁷, R⁸, R¹⁰, R¹², R¹⁴, R¹⁶ andR¹⁸ are the same or different in each repeating unit and are eachindependently hydrogen, fluorine, a hydroxy group, a thiol group, asubstituted or unsubstituted C1 to C30 carboxyl group, or a substitutedor unsubstituted C1 to C30 aliphatic organic group, R⁹, R¹¹, R¹³, R¹⁵,R¹⁷, R¹⁹, R²⁰ and R²¹ are the same or different in each repeating unitand are each independently hydrogen, substituted or unsubstituted C1 toC30 alkyl, a substituted or unsubstituted C1 to C30 carboxyl group, ahydroxy group, or a thiol group, n9, n11 and n13 are each independentlyan integer ranging from 0 to 11, and n6, n7, n8, n10, n12, n14, n15 andn16 are each independently an integer ranging from 0 to 3 and Y¹ and Y²are the same or different and are each independently a substituted orunsubstituted C6 to C30 aromatic organic group, a substituted orunsubstituted divalent to hexavalent C1 to C30 aliphatic organic group,or substituted or unsubstituted divalent to hexavalent C3 to C30alicyclic organic group; (B) a dissolution controlling agent including anovolac resin including a repeating unit represented by the followingChemical Formula 4

wherein, in Chemical Formula 4, R³ is the same or different in eachrepeating unit and is each independently a substituted or unsubstitutedC1 to C20 aliphatic organic group, and wherein greater than or equal toabout 50 mol % of R³ based on 100 mol % of R³ in a repeating unitincluded in the novolac resin is present in a meta position with respectto a hydroxy group (OH); (C) a photosensitive diazoquinone compound; (D)a silane compound; (E) an acid generator; and (F) a solvent.
 3. Thepositive photosensitive resin composition of claim 1, wherein greaterthan or equal to about 60 mol % of R³ based on 100 mol % of R³ in arepeating unit included in the novolac resin is present in a metaposition with respect to a hydroxy group (OH).
 4. The positivephotosensitive resin composition of claim 1, wherein greater than orequal to about 90 mol % of R³ based on 100 mol % of R³ in a repeatingunit included in the novolac resin is present in a meta position and apara position with respect to a hydroxy group (OH).
 5. The positivephotosensitive resin composition of claim 1, wherein R³ in a repeatingunit included in the novolac resin has a mole ratio of R³ present in ameta position (R³ _(m)) and R³ present in a para position (R³ _(p)) ofabout 5:5 to about 10:0.
 6. The positive photosensitive resincomposition of claim 1, wherein R3 in a repeating unit included in thenovolac resin has a mole ratio of R³ present in a meta position (R³_(m)) and R³ present in a para position (R³ _(p)) of about 6:4 to about9:1.
 7. The positive photosensitive resin composition of claim 1,wherein the solvent comprises γ-butyrolactone, ethyl lactate andpropylene glycol monomethylether.
 8. The positive photosensitive resincomposition of claim 1, wherein the first polybenzoxazole precursorcomprises a repeating unit represented by above Chemical Formula 1 and arepeating unit represented by above Chemical Formula 2 at a mole ratioof about 60:40 to about 95:5.
 9. The positive photosensitive resincomposition of claim 1, wherein the first polybenzoxazole precursor hasa weight average molecular weight (Mw) of about 4,000 g/mol to about20,000 g/mol.
 10. The positive photosensitive resin composition of claim1, wherein the polybenzoxazole precursor further comprises a secondpolybenzoxazole precursor including a repeating unit represented by thefollowing Chemical Formula 33, and having a thermally polymerizablefunctional group at at least one of the terminal end:

wherein, in Chemical Formula 33, X⁴ is the same or different in eachrepeating unit and is each independently a substituted or unsubstitutedC6 to C30 aromatic organic group, a substituted or unsubstitutedtetravalent to hexavalent C1 to C30 aliphatic organic group, or asubstituted or unsubstituted tetravalent to hexavalent C3 to C30alicyclic organic group, and Y⁴ is the same or different in eachrepeating unit and is each independently a substituted or unsubstitutedC6 to C30 aromatic organic group, a substituted or unsubstituteddivalent to hexavalent C1 to C30 aliphatic organic group, or asubstituted or unsubstituted divalent to hexavalent C3 to C30 alicyclicorganic group.
 11. The positive photosensitive resin composition ofclaim 10, wherein the second polybenzoxazole precursor has a weightaverage molecular weight (Mw) of about 4,000 g/mol to about 20,000g/mol.
 12. The positive photosensitive resin composition of claim 10,wherein the polybenzoxazole precursor comprises the firstpolybenzoxazole precursor and the second polybenzoxazole precursor at aweight ratio of about 5:95 to about 95:5.
 13. The positivephotosensitive resin composition of claim 1, wherein the positivephotosensitive resin composition comprises: about 1 part by weight toabout 30 parts by weight of the dissolution controlling agent (B); about5 parts by weight to about 100 parts by weight of the photosensitivediazoquinone compound (C); about 0.1 parts by weight to about 30 partsby weight of the silane compound (D); about 0.1 parts by weight to about20 parts by weight of the acid generator (E); and about 50 parts byweight to about 900 parts by weight of the solvent (F) based on about100 parts by weight of the polybenzoxazole precursor (A).
 14. Aphotosensitive resin film fabricated the positive photosensitive resincomposition according to claim
 1. 15. A semiconductor device comprisingthe photosensitive resin layer according to claim
 14. 16. Thesemiconductor device of claim 15, wherein the semiconductor device is anorganic light emitting diode (OLED) or liquid crystal display (LCD).